Crystal structure of (Z)-3-(4-meth­oxy­benzyl­idene)-2,3-di­hydro­benzo[b][1,4]thia­zepin-4(5H)-one

In the title compound, C₁₇H₁₅NO₂S, the two C atoms linking the S and carbonyl C atoms of the seven-membered thia­zepine ring are disordered over two sites, with occupancies of 0.511 (4) and 0.489 (4); both disorder components adopt distorted twist-boat conformations. In the crystal, N—H...O and C—H...O hydrogen bonds link inverted-related mol­ecules into dimers, incorporating R₁²(6) and R₂²(8) ring motifs; the acceptor carbonyl O atom is bifurcated. These dimers are further linked by C—H...O hydrogen bonds, forming supra­molecular tapes running along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.045
• wR factor = 0.139
• Data-to-parameter ratio = 19.5

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          7 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1     --  C1A     ..        6.3 su
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C10    --  C9A     ..        7.5 su
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         10 Note
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         24 Check
              C9B  -C8   -C9A     1.555   1.555   1.555             27.63 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         25 Check
              C9A  -C10  -C9B     1.555   1.555   1.555             31.63 Deg.
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... #         34 Check
              H10A -C10  -H10B    1.555   1.555   1.555             38.20 Deg.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         32 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   0 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  15 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Structural commentary

The title compound is used as an inter­mediate for the synthesis of dosulepin, which is an anti­depressant of the tricyclic family. Dosulepin prevents reabsorbing of serotonin and noradrenaline in the brain, helps to prolong the mood lightening effect of any released noradrenaline and serotonin, thus relieving depression. Dibenzo[c,e]thia­zepin derivatives exhibit chiroptical properties (Tomascovic et al., 2000). Dibenzo[b,e]thia­zepin-5,5-dioxide derivatives possess anti­histaminic and anti­allergenic activities (Rajsner et al., 1971). Benzene thia­zepin derivatives are identified as a type of effective anti­histaminic compounds (Metys et al., 1965). In view of this biological importance, the crystal structure of the title compound has been carried out and the results are presented here.

Fig. 1 shows a displacement ellipsoid plot of (I), with the atom numbering scheme. The geometric parameters of the title molecule agree well with those reported for similar structures (Selvakumar et al.., 2012; Lakshmanan et al., 2012). The sum of angles at N1 atom of the thia­zepin ring (359.9°) is in accordance with sp² hybridization. Both the major and minor conformers of the disorderd thia­zepine ring adopt distorted twist-boat conformations.

In the crystal, inter­molecular bifurcated acceptor N1—H1···O1ⁱ and C6—H6···O1ⁱ (Table 1) hydrogen bonds link inverted-related molecules into dimers, incorporating R₁²(6) and R₂²(8) ring motifs. These dimers are further linked by C1B—H1C···O1ⁱⁱ (Table 1) hydrogen bonds forming supra­molecular tapes running along the a axis (Fig. 2).

S2. Synthesis and crystallization

A mixture of (Z)-methyl 2-(bromo­methyl)-3-(4-meth­oxy­phenyl)­acrylate (2 mmol) and o-amino­thio­phenol (2 mmol) in the presence of potassium tert-butoxide (4.8 mmol) in dry THF (10 ml) was stirred at room temperature for 1 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (20 ml) and extracted with ethyl acetate (3 x 20 ml). The organic layer was washed with brine (2 x 20 ml) and dried over anhydrous sodium sulfate. It was then concentrated to successfully provide the crude final product ((Z)-3-(4-meth­oxy­benzyl­idene)-2,3-di­hydro­benzo[b][1,4] thia­zepin-4(5H)-one). This was purified by column chromatography on silica gel with ethyl­acetate/hexane 1:19 as eluent to afford the title compound in good yield (47 %). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of its ethyl­acetate solution at room temperature.

S3. Refinement

Atoms C1 and C9 of the thia­zepine ring are disordered over two positions (C1A/C1B and C9A/C9B) with refined occupancies of 0.511 (4) and 0.489 (4). The corresponding bond distances involving the disorderd atoms were restrained to be equal. H atoms were positioned geometrically, (C—H = 0.93–0.97 Å and N—H = 0.86 Å) constrained to ride on their parent atom, with U_iso(H)=1.5U_eq for methyl H atoms and 1.2U_eq(C) for other H atoms.

Related literature

For the pharmaceutical properties of thiazepin derivatives, see: Lončar-Tomascovic et al. (2000); Rajsner et al. (1971); Metys & Metysová (1965). For related structures, see: Lakshmanan et al. (2012); Selvakumar et al. (2012).

Structure description

The title compound is used as an inter­mediate for the synthesis of dosulepin, which is an anti­depressant of the tricyclic family. Dosulepin prevents reabsorbing of serotonin and noradrenaline in the brain, helps to prolong the mood lightening effect of any released noradrenaline and serotonin, thus relieving depression. Dibenzo[c,e]thia­zepin derivatives exhibit chiroptical properties (Tomascovic et al., 2000). Dibenzo[b,e]thia­zepin-5,5-dioxide derivatives possess anti­histaminic and anti­allergenic activities (Rajsner et al., 1971). Benzene thia­zepin derivatives are identified as a type of effective anti­histaminic compounds (Metys et al., 1965). In view of this biological importance, the crystal structure of the title compound has been carried out and the results are presented here.

Fig. 1 shows a displacement ellipsoid plot of (I), with the atom numbering scheme. The geometric parameters of the title molecule agree well with those reported for similar structures (Selvakumar et al.., 2012; Lakshmanan et al., 2012). The sum of angles at N1 atom of the thia­zepin ring (359.9°) is in accordance with sp² hybridization. Both the major and minor conformers of the disorderd thia­zepine ring adopt distorted twist-boat conformations.

In the crystal, inter­molecular bifurcated acceptor N1—H1···O1ⁱ and C6—H6···O1ⁱ (Table 1) hydrogen bonds link inverted-related molecules into dimers, incorporating R₁²(6) and R₂²(8) ring motifs. These dimers are further linked by C1B—H1C···O1ⁱⁱ (Table 1) hydrogen bonds forming supra­molecular tapes running along the a axis (Fig. 2).

For the pharmaceutical properties of thiazepin derivatives, see: Lončar-Tomascovic et al. (2000); Rajsner et al. (1971); Metys & Metysová (1965). For related structures, see: Lakshmanan et al. (2012); Selvakumar et al. (2012).

Synthesis and crystallization

A mixture of (Z)-methyl 2-(bromo­methyl)-3-(4-meth­oxy­phenyl)­acrylate (2 mmol) and o-amino­thio­phenol (2 mmol) in the presence of potassium tert-butoxide (4.8 mmol) in dry THF (10 ml) was stirred at room temperature for 1 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (20 ml) and extracted with ethyl acetate (3 x 20 ml). The organic layer was washed with brine (2 x 20 ml) and dried over anhydrous sodium sulfate. It was then concentrated to successfully provide the crude final product ((Z)-3-(4-meth­oxy­benzyl­idene)-2,3-di­hydro­benzo[b][1,4] thia­zepin-4(5H)-one). This was purified by column chromatography on silica gel with ethyl­acetate/hexane 1:19 as eluent to afford the title compound in good yield (47 %). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of its ethyl­acetate solution at room temperature.

Refinement details

Atoms C1 and C9 of the thia­zepine ring are disordered over two positions (C1A/C1B and C9A/C9B) with refined occupancies of 0.511 (4) and 0.489 (4). The corresponding bond distances involving the disorderd atoms were restrained to be equal. H atoms were positioned geometrically, (C—H = 0.93–0.97 Å and N—H = 0.86 Å) constrained to ride on their parent atom, with U_iso(H)=1.5U_eq for methyl H atoms and 1.2U_eq(C) for other H atoms.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. Molecular structure of the title compound showing displacement ellipsoids at the 30% probability level. H atoms are presented as a small spheres of arbitrary radii.
	Fig. 2. Supramolecular tape formation in the crystal packing of the title compound whereby bifurcated hydrogen bonds link inverted molecules into dimers sustained by N—H···O and C—H···O (red dashed lines) contacts are linked via C—H···O contacts (blue dashed lines) along a axis. [Symmetry code: (i) -x, -y, -z; (ii) x, 1+y, z].

(Z)-3-(4-Methoxybenzylidene)-2,3-dihydrobenzo[b][1,4]thiazepin-4(5H)-one

Crystal data

C17H15NO2S	F(000) = 1248
Mr = 297.36	Dx = 1.377 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4132 reflections
a = 21.434 (5) Å	θ = 1.7–29.9°
b = 5.715 (4) Å	µ = 0.23 mm^−1
c = 23.870 (5) Å	T = 293 K
β = 101.091 (4)°	Block, colourless
V = 2869 (2) Å^3	0.30 × 0.30 × 0.25 mm
Z = 8

Data collection

Bruker APEXII CCD diffractometer	4099 independent reflections
Radiation source: fine-focus sealed tube	2744 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 10.0 pixels mm^-1	θmax = 29.9°, θmin = 1.7°
ω scans	h = −30→24
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −7→8
Tmin = 0.934, Tmax = 0.944	l = −33→32
17286 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0647P)^2 + 1.1615P] where P = (Fo^2 + 2Fc^2)/3
4099 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.25 e Å^−3
4 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C2	−0.05513 (8)	0.5769 (3)	0.10567 (7)	0.0516 (4)
C3	−0.09963 (11)	0.7568 (3)	0.10107 (9)	0.0689 (5)
H3	−0.1001	0.8512	0.1327	0.083*
C4	−0.14266 (12)	0.8004 (4)	0.05193 (10)	0.0790 (6)
H4	−0.1718	0.9219	0.0503	0.095*
C5	−0.14211 (10)	0.6629 (4)	0.00527 (10)	0.0722 (5)
H5	−0.1708	0.6906	−0.0286	0.087*
C6	−0.09941 (10)	0.4851 (4)	0.00854 (9)	0.0691 (5)
H6	−0.0996	0.3927	−0.0236	0.083*
C7	−0.05515 (8)	0.4357 (3)	0.05837 (8)	0.0525 (4)
C8	0.03347 (9)	0.1194 (3)	0.08459 (7)	0.0549 (4)
C10	0.10676 (9)	0.0681 (3)	0.17287 (7)	0.0528 (4)
H10A	0.1284	−0.0130	0.1487	0.063*	0.489 (4)
H10B	0.1093	−0.0785	0.1566	0.063*	0.511 (4)
C11	0.14272 (8)	0.0921 (3)	0.23129 (7)	0.0474 (4)
C12	0.13743 (8)	0.2801 (3)	0.26731 (7)	0.0534 (4)
H12	0.1074	0.3957	0.2549	0.064*
C13	0.17552 (8)	0.2999 (3)	0.32082 (7)	0.0525 (4)
H13	0.1710	0.4276	0.3439	0.063*
C14	0.22010 (8)	0.1302 (3)	0.33987 (7)	0.0492 (4)
C15	0.22513 (8)	−0.0627 (3)	0.30585 (8)	0.0551 (4)
H15	0.2542	−0.1806	0.3190	0.066*
C16	0.18736 (8)	−0.0793 (3)	0.25292 (8)	0.0533 (4)
H16	0.1915	−0.2093	0.2305	0.064*
C17	0.26254 (13)	0.3437 (5)	0.42387 (10)	0.0895 (7)
H17A	0.2716	0.4752	0.4017	0.134*
H17B	0.2950	0.3305	0.4576	0.134*
H17C	0.2220	0.3656	0.4346	0.134*
N1	−0.01563 (7)	0.2418 (3)	0.05307 (6)	0.0610 (4)
H1	−0.0258	0.1826	0.0194	0.073*
O1	0.05465 (6)	−0.0461 (2)	0.06174 (5)	0.0605 (3)
O2	0.26115 (6)	0.1372 (2)	0.39107 (6)	0.0691 (4)
S1	−0.00374 (3)	0.55138 (8)	0.17212 (2)	0.06381 (18)
C1A	0.00694 (16)	0.2393 (5)	0.18212 (13)	0.0438 (8)	0.489 (4)
H1A	0.0222	0.2080	0.2224	0.053*	0.489 (4)
H1B	−0.0340	0.1629	0.1710	0.053*	0.489 (4)
C9A	0.05207 (17)	0.1363 (7)	0.14902 (14)	0.0425 (8)	0.489 (4)
C1B	0.06528 (16)	0.4832 (6)	0.14859 (14)	0.0529 (9)	0.511 (4)
H1C	0.0661	0.5669	0.1134	0.063*	0.511 (4)
H1D	0.1016	0.5338	0.1768	0.063*	0.511 (4)
C9B	0.07040 (18)	0.2265 (6)	0.13852 (15)	0.0467 (8)	0.511 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0612 (10)	0.0418 (8)	0.0559 (9)	−0.0078 (7)	0.0218 (8)	−0.0015 (7)
C3	0.0945 (15)	0.0501 (10)	0.0679 (12)	0.0085 (10)	0.0301 (11)	0.0005 (9)
C4	0.0937 (16)	0.0612 (12)	0.0861 (15)	0.0218 (11)	0.0275 (13)	0.0105 (11)
C5	0.0695 (12)	0.0685 (13)	0.0761 (13)	0.0072 (10)	0.0079 (10)	0.0050 (11)
C6	0.0674 (12)	0.0676 (12)	0.0677 (12)	0.0064 (10)	0.0018 (9)	−0.0141 (10)
C7	0.0505 (9)	0.0505 (9)	0.0570 (9)	−0.0039 (7)	0.0117 (7)	−0.0085 (7)
C8	0.0606 (10)	0.0570 (10)	0.0470 (9)	0.0012 (8)	0.0105 (8)	−0.0085 (7)
C10	0.0680 (11)	0.0419 (8)	0.0494 (9)	−0.0073 (8)	0.0134 (8)	−0.0044 (7)
C11	0.0530 (9)	0.0431 (8)	0.0481 (8)	−0.0056 (7)	0.0147 (7)	−0.0008 (6)
C12	0.0564 (10)	0.0456 (9)	0.0562 (9)	0.0089 (7)	0.0060 (8)	−0.0005 (7)
C13	0.0556 (10)	0.0487 (9)	0.0530 (9)	0.0055 (7)	0.0097 (7)	−0.0071 (7)
C14	0.0464 (8)	0.0509 (9)	0.0514 (9)	0.0014 (7)	0.0122 (7)	0.0047 (7)
C15	0.0538 (10)	0.0464 (9)	0.0658 (11)	0.0106 (7)	0.0135 (8)	0.0047 (8)
C16	0.0601 (10)	0.0418 (8)	0.0614 (10)	0.0026 (7)	0.0200 (8)	−0.0054 (7)
C17	0.1079 (18)	0.0866 (16)	0.0624 (12)	0.0135 (14)	−0.0125 (12)	−0.0123 (12)
N1	0.0660 (9)	0.0634 (9)	0.0499 (8)	0.0091 (7)	0.0020 (7)	−0.0183 (7)
O1	0.0781 (8)	0.0546 (7)	0.0481 (7)	0.0079 (6)	0.0104 (6)	−0.0085 (5)
O2	0.0680 (8)	0.0720 (9)	0.0597 (8)	0.0116 (7)	−0.0064 (6)	0.0002 (7)
S1	0.0906 (4)	0.0514 (3)	0.0512 (3)	−0.0002 (2)	0.0179 (2)	−0.00693 (19)
C1A	0.0543 (18)	0.0415 (16)	0.0383 (15)	−0.0025 (13)	0.0156 (13)	−0.0022 (12)
C9A	0.048 (2)	0.0385 (18)	0.0434 (17)	−0.0072 (15)	0.0143 (15)	−0.0046 (14)
C1B	0.063 (2)	0.0443 (17)	0.0482 (17)	−0.0116 (14)	0.0023 (15)	0.0032 (13)
C9B	0.0474 (19)	0.0451 (19)	0.0477 (18)	−0.0094 (15)	0.0093 (15)	−0.0068 (15)

Geometric parameters (Å, º)

C2—C7	1.388 (2)	C12—C13	1.382 (2)
C2—C3	1.392 (3)	C12—H12	0.9300
C2—S1	1.7545 (19)	C13—C14	1.376 (2)
C3—C4	1.368 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—O2	1.362 (2)
C4—C5	1.365 (3)	C14—C15	1.386 (2)
C4—H4	0.9300	C15—C16	1.367 (2)
C5—C6	1.360 (3)	C15—H15	0.9300
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.400 (3)	C17—O2	1.413 (3)
C6—H6	0.9300	C17—H17A	0.9600
C7—N1	1.415 (2)	C17—H17B	0.9600
C8—O1	1.222 (2)	C17—H17C	0.9600
C8—N1	1.363 (2)	N1—H1	0.8600
C8—C9B	1.505 (4)	S1—C1B	1.725 (3)
C8—C9A	1.516 (4)	S1—C1A	1.808 (3)
C10—C9A	1.262 (4)	C1A—C9A	1.484 (4)
C10—C9B	1.361 (4)	C1A—H1A	0.9700
C10—C11	1.464 (2)	C1A—H1B	0.9700
C10—H10A	0.9300	C1B—C9B	1.494 (4)
C10—H10B	0.9300	C1B—H1C	0.9700
C11—C12	1.395 (2)	C1B—H1D	0.9700
C11—C16	1.397 (2)
C7—C2—C3	118.18 (18)	C12—C13—H13	120.1
C7—C2—S1	126.08 (14)	O2—C14—C13	124.28 (16)
C3—C2—S1	115.74 (14)	O2—C14—C15	116.08 (15)
C4—C3—C2	122.73 (19)	C13—C14—C15	119.64 (16)
C4—C3—H3	118.6	C16—C15—C14	119.87 (15)
C2—C3—H3	118.6	C16—C15—H15	120.1
C5—C4—C3	119.0 (2)	C14—C15—H15	120.1
C5—C4—H4	120.5	C15—C16—C11	122.34 (16)
C3—C4—H4	120.5	C15—C16—H16	118.8
C6—C5—C4	119.7 (2)	C11—C16—H16	118.8
C6—C5—H5	120.2	O2—C17—H17A	109.5
C4—C5—H5	120.2	O2—C17—H17B	109.5
C5—C6—C7	122.6 (2)	H17A—C17—H17B	109.5
C5—C6—H6	118.7	O2—C17—H17C	109.5
C7—C6—H6	118.7	H17A—C17—H17C	109.5
C2—C7—C6	117.89 (17)	H17B—C17—H17C	109.5
C2—C7—N1	128.43 (17)	C8—N1—C7	139.85 (15)
C6—C7—N1	113.67 (16)	C8—N1—H1	110.1
O1—C8—N1	117.68 (15)	C7—N1—H1	110.1
O1—C8—C9B	121.1 (2)	C14—O2—C17	117.57 (15)
N1—C8—C9B	119.10 (19)	C1B—S1—C2	98.80 (12)
O1—C8—C9A	117.03 (19)	C1B—S1—C1A	74.06 (15)
N1—C8—C9A	123.48 (18)	C2—S1—C1A	104.06 (12)
C9B—C8—C9A	27.63 (14)	C9A—C1A—S1	113.6 (2)
C9A—C10—C9B	31.63 (17)	C9A—C1A—H1A	108.8
C9A—C10—C11	132.4 (2)	S1—C1A—H1A	108.8
C9B—C10—C11	130.31 (19)	C9A—C1A—H1B	108.8
C9A—C10—H10A	113.8	S1—C1A—H1B	108.8
C9B—C10—H10A	104.7	H1A—C1A—H1B	107.7
C11—C10—H10A	113.8	C10—C9A—C1A	121.8 (3)
C9A—C10—H10B	102.4	C10—C9A—C8	118.6 (2)
C9B—C10—H10B	114.8	C1A—C9A—C8	119.6 (3)
C11—C10—H10B	114.9	C9B—C1B—S1	111.6 (2)
H10A—C10—H10B	38.2	C9B—C1B—H1C	109.3
C12—C11—C16	116.35 (16)	S1—C1B—H1C	109.3
C12—C11—C10	124.67 (15)	C9B—C1B—H1D	109.3
C16—C11—C10	118.94 (15)	S1—C1B—H1D	109.3
C13—C12—C11	121.95 (16)	H1C—C1B—H1D	108.0
C13—C12—H12	119.0	C10—C9B—C1B	127.4 (3)
C11—C12—H12	119.0	C10—C9B—C8	113.0 (2)
C14—C13—C12	119.80 (16)	C1B—C9B—C8	119.6 (3)
C14—C13—H13	120.1
C7—C2—C3—C4	−0.6 (3)	C7—C2—S1—C1B	39.04 (18)
S1—C2—C3—C4	179.50 (17)	C3—C2—S1—C1B	−141.03 (17)
C2—C3—C4—C5	−0.1 (3)	C7—C2—S1—C1A	−36.62 (18)
C3—C4—C5—C6	0.5 (3)	C3—C2—S1—C1A	143.31 (16)
C4—C5—C6—C7	−0.1 (4)	C1B—S1—C1A—C9A	−17.3 (2)
C3—C2—C7—C6	0.9 (3)	C2—S1—C1A—C9A	78.0 (2)
S1—C2—C7—C6	−179.14 (14)	C9B—C10—C9A—C1A	−109.5 (6)
C3—C2—C7—N1	−178.87 (18)	C11—C10—C9A—C1A	−8.6 (6)
S1—C2—C7—N1	1.1 (3)	C9B—C10—C9A—C8	68.3 (4)
C5—C6—C7—C2	−0.6 (3)	C11—C10—C9A—C8	169.3 (2)
C5—C6—C7—N1	179.2 (2)	S1—C1A—C9A—C10	107.7 (4)
C9A—C10—C11—C12	−30.8 (4)	S1—C1A—C9A—C8	−70.1 (4)
C9B—C10—C11—C12	11.7 (4)	O1—C8—C9A—C10	34.1 (4)
C9A—C10—C11—C16	151.4 (3)	N1—C8—C9A—C10	−161.6 (3)
C9B—C10—C11—C16	−166.1 (3)	C9B—C8—C9A—C10	−71.9 (4)
C16—C11—C12—C13	1.9 (2)	O1—C8—C9A—C1A	−148.0 (3)
C10—C11—C12—C13	−175.93 (16)	N1—C8—C9A—C1A	16.3 (4)
C11—C12—C13—C14	−0.2 (3)	C9B—C8—C9A—C1A	105.9 (6)
C12—C13—C14—O2	177.88 (16)	C2—S1—C1B—C9B	−85.8 (2)
C12—C13—C14—C15	−1.9 (3)	C1A—S1—C1B—C9B	16.4 (2)
O2—C14—C15—C16	−177.57 (15)	C9A—C10—C9B—C1B	118.0 (6)
C13—C14—C15—C16	2.2 (3)	C11—C10—C9B—C1B	10.1 (6)
C14—C15—C16—C11	−0.4 (3)	C9A—C10—C9B—C8	−63.2 (4)
C12—C11—C16—C15	−1.6 (2)	C11—C10—C9B—C8	−171.13 (19)
C10—C11—C16—C15	176.40 (16)	S1—C1B—C9B—C10	−102.3 (4)
O1—C8—N1—C7	−179.9 (2)	S1—C1B—C9B—C8	79.0 (4)
C9B—C8—N1—C7	−16.1 (4)	O1—C8—C9B—C10	−32.2 (4)
C9A—C8—N1—C7	15.9 (4)	N1—C8—C9B—C10	164.6 (2)
C2—C7—N1—C8	−1.1 (4)	C9A—C8—C9B—C10	57.2 (4)
C6—C7—N1—C8	179.1 (2)	O1—C8—C9B—C1B	146.6 (3)
C13—C14—O2—C17	−7.0 (3)	N1—C8—C9B—C1B	−16.6 (4)
C15—C14—O2—C17	172.7 (2)	C9A—C8—C9B—C1B	−123.9 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	2.07	2.9291 (18)	177
C6—H6···O1^i	0.93	2.45	3.263 (3)	146
C1B—H1C···O1^ii	0.97	2.52	3.377 (4)	147

Symmetry codes: (i) −x, −y, −z; (ii) x, y+1, z.